Application of a hydroxylamine nitrate stability model to plutonium purification process equipment

A mathematical model that predicts hydroxylamine nitrate (HAN) (NH₂OH·HNO₃) stability is applied to aqueous solutions containing HAN, nitric acid and plutonium that are used in plutonium purification processes. The model estimates the stability of these solutions with respect to the rapid, hazardous, autocatalytic reaction of HAN with nitric acid that generates heat and gas. It also accounts for reaction kinetics, temperature changes, gas generation rates, solution volumes and flow rates, and distribution of plutonium and nitric acid between aqueous and organic phases. The model is applied to three typical process vessels used in solvent extraction purification of plutonium – a countercurrent aqueous/organic plutonium stripping column, an oxidation column used for HAN and hydrazine destruction, and a plutonium rework tank. Both normal and off-normal process scenarios are modeled. Two of the off-normal scenarios lead to the rapid autocatalytic reaction of HAN with nitric acid where heat and gas are generated and that could lead to damage of the process equipment and/or release of hazardous plutonium solution from the vessel. In these two cases, stationary aqueous solutions containing HAN, Pu(III), and nitric acid were allowed to slowly react until conditions for the autocatalytic reaction were reached.     

Calorimetric behaviors of hydroxylamine and its salts caused by Fe(III)

The objective of this study is to obtain information on the calorimetric behaviors of aqueous solutions of hydroxylamine (HA), hydroxylamine chloride (HACl), and hydroxylamine nitrate(HAN) caused by different Fe(III) states (free Fe(III) from Fe(NH₄)(SO₄)₂, Fe(CN)₆³⁻, and Fe(EDTA)⁻). The calorimetric data were obtained with a small-scaled reaction calorimeter, Super-CRC.

In the mixing with Fe(III), HA showed the highest reactivity among three substrates. Free Fe(III) and Fe(EDTA)⁻ showed catalytic effects in the reactions. In the overall heat of reactions, Fe(EDTA)⁻ exceeded free Fe(III), which precipitated as Fe(OH)₃ and decreased the chances of interactions with HA. It was suggested that the generation of NH₃ had taken place in the process of reducing HA along with Fe(II) oxidation. Fe(CN)₆³⁻ was less reactive than free Fe(III) and Fe(EDTA)⁻.

The ability of masking Fe(III) was estimated for CyDTA. The HA including CyDTA had no exothermic peak; however, there was an endothermic peak of the heat flow at Fe(III) injection. CyDTA was found to have the ability to inhibit a violent exothermic reaction of HA.     

Thermal explosion of autocatalytic reaction

Analytical and numerical solutions are used to determine the critical conditions for thermal explosion of autocatalytic reaction. The solutions covers both the reaction governed by the Arrhenius kinetics equation and the Frank-Kamenetskii approximation for that equation. The definition of criticality as the point at which d²θ/dβ²=0, d³θ/dβ³=0 and dθ/dβ〉0 is used here. The study is dealt with low and high exothermicity (B) of the reaction and their effects on the critical parameters. The numerical solutions cover the whole reaction from start at β = 0 up to the end at β = 1.0. All trajectories from subcritical, critical to supercritical are offered. The effects of different parameters such as B, ψ and θ_a (ambient temperature) on the critical conditions are presented. The results showed that the lower the autocatalytic factor (β₀) is, the pronounced autocatalytic reaction explosion. The analytical solution offered analytical expressions for the critical condition and the different limits of the solutions are clarified. It was found that the numerical results confirm the analytical solution.     

Detailed thermal and kinetic modeling of cumene hydroperoxide decomposition in cumene

The characterization of thermal decomposition of cumene hydroperoxide (CHP) in cumene from kinetic point of view is of great interest for industrial applications. However, the efforts done so far by the researchers lead only to the availability of single kinetic laws (first order, autocatalytic, etc.) whose usefulness is strongly limited by the presence in the starting solutions of some impurities. A detailed model aiming at simulating both, thermal and kinetic behavior of the system, is now presented. In other words, the proposed model tries to simulate CHP thermal decomposition process at varying reaction conditions (different initial temperature, in the range 120–160 °C, different initial CHP concentrations, addition of α-methylstyrene to CHP solutions in cumene) and during isothermal, scanning and adiabatic runs. A good capability of the model is observed to simulate the system behavior by using data collected under isothermal and adiabatic conditions and during scanning calorimetric runs. It is important to stress that the use of the model proposed in the present investigation does not require the adoption of adjustable parameters.     

硝酸甲胺反应过程的安全性研究

用反应量热仪(RC1e)对硝酸溶液与一甲胺溶液在反应过程中的热安定性进行初步研究,分别测试不同反应温度、加料速度和初始硝酸浓度下反应的放热情况。实验结果表明:该中和过程反应迅速,在室温就能进行;与反应温度、加料速度相比,起始硝酸浓度对反应安全性影响最大,且硝酸浓度越高,反应的速度和反应的完全程度也越高。实验还表明:RC1e是研究反应过程中热安定性情况的有效工具,能通过反应过程的热量变化体现反应速率,所得结果对硝酸甲胺的工业化生产具有重要的参考价值。     

Dilute Acid Hydrolysis of Cellulose and Cellulosic Bio-Waste Using a Microwave Reactor System

The dilute acid hydrolysis of grass and cellulose with phosphoric acid was undertaken in a microwave reactor system. The experimental data and reaction kinetic analysis indicate that this is a potential process for cellulose and hemi-cellulose hydrolysis, due to a rapid hydrolysis reaction at moderate temperatures. The optimum conditions for grass hydrolysis were found to be 2.5% phosphoric acid at a temperature of 175°C. It was found that sugar degradation occurred at acid concentrations greater than 2.5% (v/v) and temperatures greater than 175°C. In a further series of experiments, the kinetics of dilute acid hydrolysis of cellulose was investigated varying phosphoric acid concentration and reaction temperatures. The experimental data indicate that the use of microwave technology can successfully facilitate dilute acid hydrolysis of cellulose allowing high yields of glucose in short reaction times. The optimum conditions gave a yield of 90% glucose. A pseudo-homogeneous consecutive first order reaction was assumed and the reaction rate constants were calculated as: k₁ = 0.0813 s⁻¹; k₂ = 0.0075 s⁻¹, which compare favourably with reaction rate constants found in conventional non-microwave reaction systems. The kinetic analysis would indicate that the primary advantages of employing microwave heating were to: achieve a high rate constant at moderate temperatures: and to prevent ‘hot spot’ formation within the reactor, which would have cause localised degradation of glucose.     

混酸中甲苯半间歇硝化过程的危险性研究

为了解甲苯在混酸中硝化的危险性,用差示扫描量热法(DSC)测试甲苯、混酸及一硝基甲苯的热分解情况,用反应量热仪(RC1e)研究搅拌速度、温度及硝酸过用率3因素对目的反应的影响。结果表明,混酸分解温度最低,而当目的反应的3因素出现异常,以及反应过程中发生冷却失效时,均可导致硝化反应体系不稳定,此时若不停止加料,并采取措施,易引起混酸的分解,进一步可引起一硝基甲苯的分解,导致严重后果。     

Thermal risk in batch reactors: Case of peracetic acid synthesis

The present paper deals with accidents risk in batch reactors. It identifies the conditions for the occurrence of a thermal runaway and develops a probabilistic approach to assess the relevant risk. It investigates also the conditions for optimal synthesis of peracetic acid (PAA) with hydrogen peroxide (HP) and acetic acid (AA). The kinetic model of reversible reaction and side reaction of PAA synthesis is used to predict reactor temperature and molar ratio of PAA by ASPEN PLUS software. A sensitivity analysis is performed under different conditions such as constant temperature or adiabatic process with different concentrations of sulfuric acid. Assuming a prior cooling system failure, the conditions for reaction runaway triggering a thermal accident are identified in the case of PAA synthesis. Monte Carlo simulations are used in order to calculate the conditional probability of accident and optimize the synthesis of PAA.     

Evaluation of multiple reactions in dilute benzoyl peroxide concentrations with additives using calorimetric technology

Benzoyl peroxide (BPO) is a typical organic peroxide widely used in food processing, particularly flour bleaching. Due to the unstable nature of the oxygen-oxygen bond in BPO, it readily reacts under even mid-low-temperature conditions. Lower concentrations of BPO are also potentially explosive, even when combined with acid or alkaline additives. Given the history of both potential and documented industrial accidents, this study investigates the thermal stability of various BPO concentrations when mixed with acid or alkaline solutions. In addition, differential and integral kinetic models were applied to verify that the apparent activation energy data from the differential scanning calorimetry experiments were valid. The results of autocatalysis reactions and nth-order reaction simulations presented characteristics consistent with the experimental findings. The findings in this paper can be used as a reference for BPO products that are mediated with either an acid or an alkaline solution during production, storage, transportation, or use.     

Evaluation of thermal hazard characteristics of four low temperature reactive azo compounds under isothermal conditions

The polymerization reaction can lower the threshold of the required energy by the initiator to improve the efficiency of the overall process reaction. Emerging polymerization initiators are also a major focus of process improvement and technological progress. Azo compounds (azos), which used in dyeing applications, are subsequently used in polymerization reactions due to their highly exothermic reaction characteristics. Although higher heat release can promote polymerization and modify the product, heat generation may also cause process hazards.These thermal hazard parameters were studied by selecting dimethyl 2,2′-azobis(2,4-dimethylvaleronitrile) (ABVN), 2,2′-azobis(2-methyl propionate) (AIBME), 2,2′-azobis(2-methylpropionamide) dihydrochloride (AIBA), and 2,2′-azobis(isobutyronitrile) (AIBN), which are common azo initiators at present. Thermal hazards are closely related to the reaction kinetics of the substance itself. The form of the reaction, the apparent activation energy and the thermodynamic parameters of the exothermic mode were also obtained.Kinetic analysis of the actual process using the experimental data of the isothermal calorimetry model is rarely used in the evaluation of related thermal hazard characteristics. The simulation results revealed the kinetic azo models and were further applied to calculate the runaway situations of azo under specific boundary conditions.     

TiO2悬浆体系光催化降解酸性红B动力学分析

采用TiO2悬浆体系, 以高硼紫外灯为光源, 考察了酸性红B 光催化降解中溶液初始质量浓度、催化剂投加量、无机盐、空气通入量、pH 值对光催化降解速率影响.用Langmuir-hinshelwood 方程描述酸性红B光催化动力学行为. 结果表明:初始质量浓度增加, 反应由一级向零级过渡; 催化剂投加量在0.5～2.5 g/L时, 30 mg/L酸性红B一级反应速率常数与投加量成线性关系; 5种溶解性无机盐对光催化降解酸性红B存在抑制作用, 阴离子影响大于阳离子; 通入空气影响动力学行为, 改变反应级数.本实验在pH 值为3时光催化降解效果最佳, 且酸性条件下比碱性下条件效果更好;TiO2表面吸附能力随pH 值增大而减弱,光催化过程控制步骤在酸性和碱性条件不同.     

高锰酸钾去除水中甲硫醚的效能及动力学研究

通过烧杯试验研究水处理常用氧化剂KMnO_4氧化水中甲硫醚的效能,探讨了KMnO_4投加量、甲硫醚初始质量浓度、p H值及腐殖酸质量浓度对氧化反应的影响,并对反应动力学及氧化产物进行了分析。结果表明:不同剂量的KMnO_4氧化甲硫醚反应在t=10 min内已基本完成,去除率达99%;随KMnO_4投加量增加,去除率和反应速率增加;KMnO_4过量条件下甲硫醚初始质量浓度对反应速率和去除率无影响;p H值对反应速率常数影响较显著,当p H=6.85时,反应速率常数达到最大;0~30 mg/L的腐殖酸对甲硫醚去除率基本无影响,但对反应速率有一定的抑制作用。腐殖酸质量浓度在0~15 mg/L变化时,反应速率常数基本不变;腐殖酸质量浓度从15 mg/L增大到20mg/L时,反应速率常数迅速变小,反应进程变慢;而当腐殖酸质量浓度大于等于20 mg/L时,反应速率常数又基本不变。KMnO_4氧化甲硫醚的反应符合二级反应动力学模型,二级反应的动力学常数k=0.647 L/(min·mg)。通过GC/MS对反应产物分析发现,KMnO_4可将甲硫醚氧化为二甲基亚砜。因此,KMnO_4是一种高效、快速的去除水中甲硫醚的氧化剂。     

HAN阻隔防爆模型研究

通过合理简化,利用多方气体状态方程,分别建立油品储运容器内可燃混合气体定容爆炸模型和装设阻隔防爆材料的油品储运容器内可燃混合气体爆炸模型,获得了阻隔防爆性能测试装置的燃爆容器抗爆设计限值,以及其在HAN阻隔防爆测试中燃爆容器试爆压力量级的控制下限值,同时,还给出HAN工程应用中容器留空率的计算方法,具有实际指导意义。     

Stable and eco-friendly solid acids as alternative to sulfuric acid in the liquid phase nitration of toluene

Liquid-phase nitration of toluene was carried out using a silica supported Cs salt of phosphomolybdic acid (Cs_2.5H_0.5PMoO₄₀) as catalyst with dilute nitric acid under mild conditions. The Cs_2.5H_0.5PMoO₄₀ particles with Keggin-type structure were well dispersed on the surface of silica, and the catalysts exhibited strong acidity, which may be responsible for the high catalytic nitration activity. The effects of various parameters on nitration were tested, which included reaction temperature, reaction time, catalyst amount and reactants ratio. Under suitable conditions, the nitrations gave high toluene conversion (99.6%) and good mono-nitration selectivity. Compared to the conventional process, there was no other organic solvent or sulfuric acid used in the reaction system, which made it more environment-friendly. Moreover, the supported catalyst was proven to have excellent stability in the nitration process.     

交联壳聚糖膜吸附直接染料的性能研究

以戊二醛为交联剂,采用流延法制备交联壳聚糖膜作为吸附剂,对3种不同直接染料水溶液进行吸附脱色处理,实验表明,刚果红的去除率可达96%,直接紫B、直接绿BE的去除率均可达81%。交联壳聚糖膜对刚果红的吸附符合Langmuir方程(R2=0.999),对直接绿和直接紫的吸附符合Freundlich方程,相关系数均大于0.99;吸附过程动力学符合二级反应,R2均为0.999。     

硫化油生产过程的活性反应危害识别与评估

利用差示扫描量热仪（DSC）、反应量热仪（RC1和快速筛选仪（RSD）等仪器设备，对硫化油合成过程的热特征和压力特征进行系统研究，发现该反应为微吸热的过程，但仍应严格控制工艺参数，如压力、温度等。防止反应器中混入水等低沸点物质，导致容器超压。反应器内避免混入空气、硝酸等禁忌物料，防止因活性反应而引发灾害性燃爆事故。     

C6H12N4+Mg+KClO4+SrSO4系统的振荡控制和安全分析

从实验和数值分析两方面研究了C6Hl2N 4+Mg+KClO4+SrSO4反应系统的振荡燃烧现象,并对反应机理进行了深层次的分析.结果表明,振荡燃烧是由化学动力学的非线性反馈引起的,即:反应系统中镁的三相与氧气的相互竞争反应造成系统的非线性化学振荡燃烧.氧化剂和可燃剂的比值,以及频率调节剂等吸热物质可调节气相镁的生成速率,能有效地控制药剂的振荡频率.选取适当的控制参数,可以使反应按照预定的、安全的过程进行,避免爆燃的产生.本文的研究结果对化工、军事等领域的安全控制具有重要意义.     

UV-Fenton 体系氧化降解苯酚废水反应动力学研究

利用UV-Fenton高级氧化技术对苯酚废水进行了处理研究.通过半衰期法对苯酚的反应级数进行了探讨,确定其在UV-Fenton体系降解过程中的表观反应级数为3/2,并初步建立了苯酚UV-Fenton降解的动力学模型,并从反应速率系数着手探讨了污染物初始浓度、双氧水加入量、亚铁离子浓度及pH值对反应降解速率的影响.     

Absorption kinetics of NO from simulated flue gas using Fe(II)EDTA solutions

The absorption of NO encountering flue gases in aqueous solutions of Fe(II)EDTA was determined using a semi-batch stirred tank with a plane gas–liquid interface at 50 °C. The concentrations of NO, SO₂ and O₂ in the feeding stream were 300–800 ppm, 500–2200 ppm and 0–20%, respectively. The pH value of the Fe(II)EDTA solutions varied from 3 to 11. The concentrations of Fe(II)EDTA were maintained between 0.01 and 0.05 M. Experiments were performed to evaluate the effect of operating parameters on the NO absorption rate, the reaction kinetics of the reactants in gas and liquid phases, and the effect of competition between various reactants on the mass transfer rate in the NO removal system. Results indicate that the average reaction rate constant is 3.70 × 10⁷ M⁻¹ s⁻¹. Adding NaOH does not increase the absorption capability of Fe(II)EDTA. The presence of O₂ decreases the NO absorption rate with Fe(II)EDTA. The absorption rate of NO with Fe(II)EDTA decreases at low concentrations of SO₂, but increases at high concentrations.     

Critical runaway conditions and stability criterion of RDX manufacture in continuous stirred tank reactor

The energetic material cyclo-1,3,5-trimethylene-2,4,6-trinitramine (RDX) has been widely used as explosive and propellant ingredients in the military industry. It is usually produced by hexamine nitration reaction in continuous stirred tank reactor (CSTR). This manufacturing process is quite dangerous and always causes fire incidents or explosion owing to its thermal instability in its nitration reaction or purification processes. In this investigation, we used its reaction kinetics parameters to evaluate the thermal hazard conditions and stable reaction criteria in the reaction systems of continuous stirred tank reactor.